Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
  • C08G75/02—Polythioethers
  • C08G75/0204—Polyarylenethioethers
  • C08G75/025—Preparatory processes
  • C08G75/0254—Preparatory processes using metal sulfides

Definitions

• Polyarylene sulphides and the production thereof are known (cf., for example, U.S. Pat. Nos. 2,538,941; 2,513,188; 3,876,592 and 3,354,129; DE-AS No. 2,453,749, DE-OS No. 2,623,363, U.S. Pat. Nos. 4,038,261; 4,038,259 and 4,038,263; DE-OS No. 2,623,362, U.S. Pat. No. 4,038,262, DE-OS 2,623,333, U.S. Pat. Nos. 4,064,114; 4,038,260 and 4,039,518; JA-OS Nos. 55-54 330 and 75-123 799, U.S. Pat. Nos. 3,117,620; 3,524,835 and 3,839,301 and DE-OS Nos. 2,930,710, 2,930,797 and 3,019,732.
• the polyarylene sulphides obtained do not have high molecular weights and are not thermoplastically processible and a hardening or curing step has to be carried out after the reaction to improve the properties of the end products by chain-extending and branching reactions.
• thermoplastically processible polyarylene sulphides are obtained by known processes (cf. DE-OS Nos. 2,930,710, 2,930,797 and 3,019,732, as cited above), it is necessary to use particular catalysts and to apply reaction temperatures which are frequently above the boiling point of the polar solvents, with the result that the reaction has to be carried out under excess pressure.
• hexamethyl phosphoric acid triamide is used as co-solvent in addition to N-methyl(2)pyrrolidone in a pressure reaction in the production of polyarylene sulphides.
• polyarylene sulphides are obtained by reacting P 2 S 5 , alkali metal or alkaline earth metal hydroxides and aromatic polyhalogen compounds in phosphoric acid amides.
• polyarylene sulphides which are not of high molecular weight are obtained in yields of less than 60%, based on the aromatic polyhalogen compound, in a pressure reaction.
• hexamethyl phosphoric acid amide is recommended as solvent for the production of polyphenylene sulphide.
• the pressure has to be kept high enough to keep the p-dihalogen benzene and the amide substantially fluid (column 2, lines 64/66).
• polyarylene sulphides may be obtained without having to apply excess pressure providing aromatic polyhalogen compounds and alkali metal sulphides are condensed in known manner in cyclic organophosphorus compounds, preferably 1-alkyl-1-oxophospholanes, optionally in the presence of a catalyst and/or a co-solvent.
• the polyarylene sulphides obtained may be moulded, extruded and spun into fibres without any need for a curing step.
• the present invention relates to a process for the production of high molecular weight, optionally branched, polyarylene sulphides from:
• (a) dihalogen benzenes from 50 to 100 mole percent of which correspond to the following general formula: ##STR1## and from 0 to 50 mole percent of which to the following general formula: ##STR2## wherein X independently represents fluorine, chlorine, bromine or iodine, preferably chlorine or bromine; and the radicals R 1 , which may be the same or different, represent hydrogen, C 1 -C 20 alkyl, C 5 -C 20 cycloalkyl, C 6 -C 24 aryl, C 7 -C 24 alkaryl or C 7 -C 24 aralkyl, and/or two of the radicals R 1 may be linked together to form an aromatic or heterocyclic ring and at least one of the radicals R 1 represents other than hydrogen; and
• Ar represents a C 6 -C 24 aromatic or heterocyclic radical
• X is defined as in general formulae (I) and (II);
• n 3 or 4;
• alkali metal sulphides preferably sodium or potassium sulphide or mixtures thereof, preferably in the form of the hydrates or aqueous mixtures, optionally together with alkali metal hydroxides, the molar ratio of (a+b):c amounting to from 0.85:1 to 1.15:1, preferably from 0.95:1 to 1.05:1; in
• an organic solvent optionally using one or more catalysts and/or co-solvents, characterised in that the molar ratio of alkali metal sulphides(s) (c) to the organic solvent (d) is from 1:2 to 1:15, cyclic organophosphorus compounds are used as the organic solvent (d) and the process is carried out over a period of up to 10 hours, at a temperature of from 160° to 240° C., preferably from 165° to 225° C., and in the absence of excess pressure.
• alkali metal fluorides for example alkali metal fluorides, alkali metal phosphates and alkali metal carboxylates, may be employed in the conventional quantities as the optional catalysts.
• the optional co-solvents may be N,N-dialkyl carboxylic acid amides of C 1 -C 18 aliphatic and or C 6 -C 12 aromatic carboxylic acids in a quantity of from 0.02 to 1.0 mole per mole of alkali metal sulphide.
• alkali metal sulphides used and the quantity in which they are used correspond to the prior art.
• Lithium, sodium, potassium and rubidium sulphide for example, are suitable, sodium sulphide and potassium sulphide being preferred.
• LiOH, NaOH and KOH may be mentioned as alkali metal hydroxides which may optionally be used for regenerating the alkali metal sulphides from any hydrogen sulphides present. It is also possible in both cases to use mixtures both of the sulphides and of the hydroxides.
• the alkali metal sulphides may be dehydrated in one or more steps, for example by distilling off the water from the reaction solution.
• the partial dehydration step should be completed before addition of the p-dihalogen compounds corresponding to general formulae (I) and (II).
• Any N,N-dialkyl carboxylic acid amides used as co-solvent are preferably introduced before dehydration of the alkali metal sulphides. However, it is possible in principle to add the co-solvents together with the polyhalogen compounds to the dehydrated mixture.
• the reactants may be combined in any form.
• the aromatic dihalogen compounds corresponding to general formulae (I) and (II) and the aromatic tri- and tetra-halogen compounds corresponding to general formula (III) may be added together or separately, continuously, in portions or all at once to the alkali metal sulphide, the solvent or a portion thereof.
• the molar ratio of aromatic meta- to para-dihalogen compounds corresponding to general formulae (I) and (II) should amount to at most 30:70.
• thermoplastically processible polyphenylene sulphides it is particularly preferred to use aromatic p-dihalogen compounds.
• aromatic dihalogen compounds corresponding to general formula (I) used in accordance with the present invention are p-difluorobenzene, p-dichlorobenzene, p-dibromobenzene, p-diiodobenzene, 1-fluoro-4-chlorobenzene, 1-fluoro-4-bromobenzene, 1-chloro-4-bromobenzene, 1-chloro-4-iodobenzene, 1-bromo-4-iodobenzene, 1,3-difluorobenzene, 1,3-dichlorobenzene, 1,3-dibromobenzene, 1,3-diiodobenzene, 1-fluoro-3-chlorobenzene, 1-fluoro-3-bromobenzene, 1-fluoro-3-iodobenzene, 1-chloro-3-bromobenzene, 1-chloro-3-iodobenzene, 1-ch
• aromatic dihalogen compounds corresponding to general formula (II) which may be used in accordance with the present invention are 2,5-dichlorotoluene, 2,5-dichloroxylene, 1-ethyl-2,5-dichlorobenzene, 1-ethyl-2,5-dibromobenzene, 1-ethyl-2-bromo-5-chlorobenzene, 1,2,4,5-tetramethyl-3,5-dichlorobenzene, 1-cyclohexyl-2,5-dichlorobenzene, 1-phenyl-2,5-dichlorobenzene, 1-benzyl-2,5-dichlorobenzene, 1-phenyl-2,5-dibromobenzene, 1-p-tolyl-2,5-dichlorobenzene, 1-p-tolyl-2,5-dibromobenzene, 1-hexyl-2,5-dichlorobenzene, 2,4-dichloroto
• Examples of the aromatic tri- or tetra-halogen compounds according to general formula (III) used in accordance with the present invention are 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene, 1,2,4-tribromobenzene, 1,2,4-triiodobenzene, 1,3,5-trichloro-2,4,6-trimethyl-benzene, 1,2,3-trichloronaphthalene, 1,2,4-trichloronaphthalene, 1,2,6-trichloronaphthalene, 2,3,4-trichlorotoluene, 2,3,6-trichlorotoluene, 1,2,3,4-tetrachloronaphthalene, 1,2,4,5-tetrachlorobenzene, 2,2',4,4'-tetrachlorobiphenyl and 1,3,5-trichlorotriazine.
• Aromatic di-, tri- and tetra-halogen compounds may be added to the reaction phase both simultaneously and also separately.
• Cyclic organophosphorus compounds suitable for use in accordance with the present invention include p-substituted phospholanes and p-substituted phosphanes.
• Suitable p-substituents include C 1 -C 8 -alkyl C 6 -C 12 aryl, C 7 -C 20 aralkyl and C 5 -C 10 cycloalkyl, preferably C 1 -C 4 alkyl.
• Cyclic organophosphorus compounds preferably used in accordance with the present invention are those corresponding to the following general formula: ##STR3## wherein R 2 represents an ⁇ , ⁇ -butylene or ⁇ , ⁇ -pentylene radical, which may be substituted, preferably an ⁇ , ⁇ -butylene radical, and
• R 3 represents a C 1 -C 8 alkyl, C 6 -C 12 aryl, C 7 -C 20 aralkyl or C 5 -C 10 cycloalkyl radical, preferably a C 1 -C 4 alkyl radical.
• Compounds corresponding to general formula (IV) preferably used in accordance with the present invention are 1-methyl-1-oxophospholane, 1-ethyl-1-oxophospholane, 1-phenyl-1-oxophospholane, 1-methyl-1-oxo-phosphane, 1-propyl-1-oxophosphane and 1-phenyl-1-oxophosphane.
• the reaction may be carried out over a period of up to 10 hours, although the reaction time is preferably from 0.2 to 8 hours. It is advantageous to increase the reaction temperature in stages during the reaction.
• reaction is carried out under atmospheric pressure. Although not necessary, excess pressure may be applied, in which case excess pressures of from 0.1 to 20 bar are suitable.
• reaction mixture may be worked-up and the polyarylene sulphides isolated by various known techniques.
• the polyarylene sulphide may be separated from the reaction solution either directly or after the addition of, for example, water and/or dilute acids using conventional procedures, for example filtration or centrifugation.
• Filtration is generally followed by washing with water in order to remove inorganic constituents, such as residues of alkali metal sulphides and alkali metal chlorides, which may adhere to the polymers.
• washing or extraction with other washing liquids which may even be carried out in addition to or after this washing step, is, of course, also possible.
• the polymer may be recovered by distilling off the solvent from the reaction zone, followed by washing in the manner described above.
• the polyarylene sulphides according to the present invention may be mixed with other polymers and with pigments and fillers, such as graphite, metal powders, glass powders, quartz powder or glass fibres, or may have the additives normally used for polyarylene sulphides, such as conventional stabilizers or mould release agents, added thereto.
• melt flow index of polyarylene sulphides is measured in accordance with ASTM 1238-70 at 316° C. using a 5 kg weight and is expressed in g/10 minutes.
• melt viscosity ⁇ m of the polymer melt was determined at 306° C. in dependence upon the shear stress (in Pa.s) by means of an Instron rotation viscosimeter.
• melt viscosity over a very wide range of from 10 -1 to 10 -7 Pa.s.
• an Instron Rheometer the polymer is melted between a fixed plate and a rotatable cone and the torque of the cone determined. It is possible to calculate melt viscosity as a function of the shear stress from the torque, the angular velocity and the apparatus data.
• An Instron Model 3250 Rheometer was used (diameter of the cone and the plate 2 cm).
• the value quoted is the melt viscosity measured at a shear stress ⁇ of 10 2 Pa.
• the p-polyarylene sulphides according to the present invention generally have melt viscosities of from 0.5 ⁇ 10 3 to 5 ⁇ 10 5 Pa.s or even higher, preferably from 1.5 ⁇ 10 3 to 10 4 Pa.s. They may be directly processed by extrusion, extrusion blowing, injection moulding or other conventional processing techniques to form for example films, mouldings or fibres which are used for example in the conventional way as automobile components, fittings, electrical components, for example switches, electronic circuit boards, components and apparatus resistant to chemicals, such as pump housings and pump flywheels, etching baths, sealing rings, parts of office machines and telex machines, as well as domestic appliances, valves, ballbearing components.
• this Example describes the production of polyphenylene sulphide in accordance with U.S. Pat. No. 3,354,129.
• this Example describes the production of p-polyphenylene sulphide in accordance with JA-PS No. 55-54 330.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

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Citations (8)

• 1982
  • 1982-04-23 DE DE19823215259 patent/DE3215259A1/de not_active Withdrawn
• 1983
  • 1983-04-11 US US06/483,627 patent/US4464507A/en not_active Expired - Fee Related
  • 1983-04-11 EP EP83103475A patent/EP0092723B1/de not_active Expired
  • 1983-04-11 DE DE8383103475T patent/DE3365981D1/de not_active Expired
  • 1983-04-19 JP JP58067916A patent/JPS58191719A/ja active Pending

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